KR102618701B1 - Multi-layer stretchable substrate for stretchable display - Google Patents
Multi-layer stretchable substrate for stretchable display Download PDFInfo
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- KR102618701B1 KR102618701B1 KR1020200177891A KR20200177891A KR102618701B1 KR 102618701 B1 KR102618701 B1 KR 102618701B1 KR 1020200177891 A KR1020200177891 A KR 1020200177891A KR 20200177891 A KR20200177891 A KR 20200177891A KR 102618701 B1 KR102618701 B1 KR 102618701B1
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- manufacturing
- stretchable
- substrate
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J7/00—Chemical treatment or coating of shaped articles made of macromolecular substances
- C08J7/04—Coating
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C55/00—Shaping by stretching, e.g. drawing through a die; Apparatus therefor
- B29C55/02—Shaping by stretching, e.g. drawing through a die; Apparatus therefor of plates or sheets
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- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/08—Processes
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- C08G18/0842—Manufacture of polymers in the presence of non-reactive compounds in the presence of liquid diluents
- C08G18/0847—Manufacture of polymers in the presence of non-reactive compounds in the presence of liquid diluents in the presence of solvents for the polymers
- C08G18/0852—Manufacture of polymers in the presence of non-reactive compounds in the presence of liquid diluents in the presence of solvents for the polymers the solvents being organic
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/2805—Compounds having only one group containing active hydrogen
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- C08G18/284—Compounds containing ester groups, e.g. oxyalkylated monocarboxylic acids
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- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/30—Low-molecular-weight compounds
- C08G18/38—Low-molecular-weight compounds having heteroatoms other than oxygen
- C08G18/3802—Low-molecular-weight compounds having heteroatoms other than oxygen having halogens
- C08G18/3804—Polyhydroxy compounds
- C08G18/3812—Polyhydroxy compounds having fluorine atoms
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- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
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- C08J5/18—Manufacture of films or sheets
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- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D175/00—Coating compositions based on polyureas or polyurethanes; Coating compositions based on derivatives of such polymers
- C09D175/04—Polyurethanes
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- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
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Abstract
본 발명은 스트레처블 디스플레이 장치에 사용되는 내오염, 내스크래치성을 가지는 스트레처블 디스플레이용 연신기판에 관한 것이다. 본 발명의 조성물 및 제조방법을 이용하면, 한 번의 코팅으로 2개의 층을 가진 스트레처블 디스플레이용 연신기판을 쉽게 제조할 수 있고, 연신 기판의 최외곽 표면에 코팅된 퍼플루오로 폴리머 코팅층에 의해 내오염성 및 내스크래치성이 도입되어 스트레처블 디스플레이 터치에 의한 표면의 손상을 막을 수 있다.The present invention relates to a stretched substrate for a stretchable display having anti-fouling and scratch resistance properties used in a stretchable display device. Using the composition and manufacturing method of the present invention, a stretched substrate for a stretchable display with two layers can be easily manufactured with a single coating, and the perfluoropolymer coating layer coated on the outermost surface of the stretched substrate can be easily manufactured. Contamination resistance and scratch resistance are introduced to prevent damage to the surface caused by touching the stretchable display.
Description
본 발명은 스트레처블 디스플레이 장치에 사용되는 내오염, 내스크래치성을 가지는 스트레처블 디스플레이용 연신기판에 관한 것이다.The present invention relates to a stretched substrate for a stretchable display having anti-fouling and scratch resistance properties used in a stretchable display device.
최근에는 LCD, OLED등의 평판 디스플레이 관련 기술이 발달하고 있으며, 접었다 펼 수 있는 폴더블 디스플레이 롤 형태로 감을 수 있는 롤러블 디스플레이와 더불어 늘리거나 줄일 수 있으며 자유로운 형태로 변화 가능한 스트레처블 디스플레이 장치에 대한 연구가 활발히 진행되고 있다. 스트레처블 디스플레이를 구현하기 위해서는 먼저 스트레처블 기판 제작에 대한 선행연구가 진행되어야 하며, 주로 PDMS(polydimethylsiloxane), PU(polyurethane)과 같은 소재들로 연구가 진행되고 있다. 최근 어플리케이션에 대한 개발이 다양화되면서 디스플레이에 터치센서를 도입하게 되면서 디스플레이 표면에 대한 내오염 및 내스크래치성의 중요성이 커지고 있다.Recently, technologies related to flat panel displays such as LCD and OLED are developing, and in addition to foldable displays that can be folded and unfolded, rollable displays that can be rolled up in the form of rolls, and stretchable display devices that can be stretched or shortened and freely change into shapes. Research is actively underway. In order to implement a stretchable display, prior research on the production of stretchable substrates must first be conducted, and research is mainly conducted with materials such as PDMS (polydimethylsiloxane) and PU (polyurethane). Recently, as the development of applications has diversified and touch sensors have been introduced to displays, the importance of anti-contamination and scratch resistance for the display surface is increasing.
최근 어플리케이션에 대한 개발이 다양화되면서 디스플레이에 터치센서를 도입하게 되면서 터치에 의한 디스플레이의 오염 혹은 스크래치에 의한 손상이 발생하여 성능이 저하되거나 디스플레이에 영구적인 고장을 일으킬 수 있다는 문제가 있었다. 이에 본 발명자들은 디스플레이 표면에 대한 내오염성 및 내스크래치성을 가진 스트레처블 디스플레이용 연신기판을 개발하고자 예의 연구 노력하였다. 그 결과, 퍼플루오로 폴리머와 연신기판 제조용 폴리머를 혼합하여 코팅을 하면, 두 가지 폴리머의 비중 차이에 의하여 한 번의 코팅으로 2층의 연신기판이 쉽게 제조될 수 있음을 규명함으로써, 본 발명을 완성하게 되었다. Recently, as the development of applications has diversified and touch sensors have been introduced to displays, there has been a problem that the display may be contaminated by touch or damaged by scratches, which may reduce performance or cause permanent damage to the display. Accordingly, the present inventors made extensive research efforts to develop a stretched substrate for a stretchable display that has stain resistance and scratch resistance on the display surface. As a result, the present invention was completed by demonstrating that when a perfluoropolymer and a polymer for manufacturing stretched substrates are mixed and coated, a two-layer stretched substrate can be easily manufactured with a single coating due to the difference in specific gravity of the two polymers. I did it.
따라서, 본 발명의 목적은 퍼플루오로 폴리머를 포함하는 코팅층; 및 연신성(stretchable)을 갖는 연신성 기판을 포함하는, 스트레처블 디스플레이용 연신기판을 제공하는 것이다. Therefore, the object of the present invention is a coating layer containing a perfluoropolymer; and a stretchable substrate having stretchability, to provide a stretchable substrate for a stretchable display.
본 발명의 다른 목적은 퍼플루오로 폴리머 및 연신성 기판 제조용 폴리머를 포함하는, 스트레처블 연신기판 제조용 조성물을 제공하는 것이다.Another object of the present invention is to provide a composition for manufacturing a stretchable substrate, including a perfluoropolymer and a polymer for manufacturing a stretchable substrate.
본 발명의 또 다른 목적은 스트레처블 디스플레이용 연신기판의 제조방법을 제공하는 것이다. Another object of the present invention is to provide a method for manufacturing a stretched substrate for a stretchable display.
본 발명의 일 양태에 따르면, 본 발명은 퍼플루오로 폴리머를 포함하는 코팅층; 및 연신성(stretchable)을 갖는 연신성 기판을 포함하는, 스트레처블 디스플레이용 연신기판을 제공한다. According to one aspect of the present invention, the present invention includes a coating layer containing a perfluoropolymer; and a stretchable substrate having stretchability.
본 발명의 일 구현예에 있어서, 상기 퍼플루오로 폴리머는 (a) 퍼플루오로 다이올; 불소계 용제; 유기용매; 모노이소시아네이트 아크릴레이트 모노머, 다이이소시아네이트 모노머, 또는 이들의 조합을 포함하는 반응 혼합물을 형성시키는 단계; 및 (b) 촉매제를 첨가하고 가열하는 중합반응 단계에 의해 생성된다. In one embodiment of the present invention, the perfluoro polymer is (a) perfluoro diol; fluorine-based solvent; organic solvent; forming a reaction mixture comprising monoisocyanate acrylate monomer, diisocyanate monomer, or a combination thereof; and (b) a polymerization reaction step of adding a catalyst and heating.
상기 퍼플루오로 폴리머의 생성 공정 (a) 및 (b) 단계는 1 내지 5회의 범위 내에서 반복 실시 가능하다. 예를 들어, 상기 공정이 1회만 실시될 경우는 1차 중합반응에 의해 퍼플루오로 폴리머가 형성되고, 상기 공정이 2회 실시될 경우에는 1차 및 2차 중합반응에 의해 퍼플루오로 폴리머가 형성된다.Steps (a) and (b) of the perfluoropolymer production process can be repeated within the range of 1 to 5 times. For example, when the above process is performed only once, a perfluoro polymer is formed through the first polymerization reaction, and when the above process is performed twice, the perfluoro polymer is formed through the first and second polymerization reactions. is formed
상기 (a) 단계의 반응혼합물은 100 내지 500 rpm, 또는 200 내지 300 rpm의 교반속도로 교반함으로써 형성되고, 교반 온도는 실온 또는 상온이다.The reaction mixture in step (a) is formed by stirring at a stirring speed of 100 to 500 rpm, or 200 to 300 rpm, and the stirring temperature is room temperature or room temperature.
상기 (b) 단계의 가열은 상온에서 시작하여 50 내지 150℃, 50 내지 120℃, 50 내지 100℃, 70 내지 150℃, 70 내지 120℃, 70 내지 100℃, 80 내지 150℃, 80 내지 120℃, 80 내지 100℃의 온도로 이루어진다.Heating in step (b) starts at room temperature and continues at 50 to 150°C, 50 to 120°C, 50 to 100°C, 70 to 150°C, 70 to 120°C, 70 to 100°C, 80 to 150°C, 80 to 120°C. ℃, consisting of a temperature of 80 to 100 ℃.
상기 퍼플루오로 폴리머의 중합반응에는 퍼플루오로 다이올 5 내지 40 중량부; 불소계 용제 30 내지 60 중량부; 모노이소시아네이트 아크릴레이트 모노머 5 내지 35 중량부 및/또는 다이이소시아네이트 모노머 5내지 35 중량부; 촉매제 0.005 내지 0.1 중량부; 및 유기용매 5 내지 15 중량부를 포함할 수 있다. In the polymerization reaction of the perfluoro polymer, 5 to 40 parts by weight of perfluoro diol; 30 to 60 parts by weight of a fluorine-based solvent; 5 to 35 parts by weight of monoisocyanate acrylate monomer and/or 5 to 35 parts by weight of diisocyanate monomer; 0.005 to 0.1 parts by weight of catalyst; and 5 to 15 parts by weight of an organic solvent.
상기 퍼플루오로 폴리머의 중합반응에는 모노이소시아네이트 아크릴레이트 모노머 25 중량부에 대하여 퍼플루오로 다이올 10 내지 40 중량부; 불소계 용제 35 내지 55 중량부; 다이이소시아네이트 모노머 5내지 30 중량부; 촉매제 0.005 내지 0.1 중량부; 및 유기용매 5 내지 15 중량부를 포함할 수 있다. The polymerization reaction of the perfluoro polymer includes 10 to 40 parts by weight of perfluoro diol based on 25 parts by weight of monoisocyanate acrylate monomer; 35 to 55 parts by weight of a fluorine-based solvent; 5 to 30 parts by weight of diisocyanate monomer; 0.005 to 0.1 parts by weight of catalyst; and 5 to 15 parts by weight of an organic solvent.
본 발명의 일 구현예에 있어서, 상기 퍼플루오로 폴리머의 중합반응에는 모노이소시아네이트 아크릴레이트 모노머 25 중량부에 대하여 퍼플루오로 다이올 10 내지 30 중량부; 불소계 용제 45 중량부; 다이이소시아네이트 모노머 5내지 25 중량부; 촉매제 0.01 내지 0.05 중량부; 및 유기용매 10 중량부를 포함한다.In one embodiment of the present invention, the polymerization reaction of the perfluoro polymer includes 10 to 30 parts by weight of perfluoro diol based on 25 parts by weight of monoisocyanate acrylate monomer; 45 parts by weight of fluorine-based solvent; 5 to 25 parts by weight of diisocyanate monomer; 0.01 to 0.05 parts by weight of catalyst; and 10 parts by weight of an organic solvent.
본 발명의 특정 구현예에 있어서, 상기 퍼플루오로 폴리머의 중합반응에는 모노이소시아네이트 아크릴레이트 모노머 25 중량부에 대하여 퍼플루오로 다이올 20 중량부; 불소계 용제 45 중량부; 다이이소시아네이트 모노머 12 중량부; 촉매제 0.02 중량부; 및 유기용매 10 중량부를 포함한다.In a specific embodiment of the present invention, the polymerization reaction of the perfluoro polymer includes 20 parts by weight of perfluoro diol based on 25 parts by weight of monoisocyanate acrylate monomer; 45 parts by weight of fluorine-based solvent; 12 parts by weight of diisocyanate monomer; 0.02 parts by weight of catalyst; and 10 parts by weight of an organic solvent.
본 발명의 일 구현예에 있어서, 상기 유기용매는 상기 고형분 성분들을 용해하기에 적합한 것이라면 제한되지 않고 사용될 수 있으며, 프로필렌글리콜 모노메틸 에테르 아세테이트(PGMEA), 프로필렌글리콜 모노메틸 에테르(PGME), 부틸셀로솔브(BC), 메틸셀로솔부(MC), 에틸렌글리콜(EG), 프로필렌글리콜(PG), N-메틸-2-피롤리돈(NMP), 디메틸아세트아미드(DMAc), 프로필렌 글리콜 디아세테이트(PGDA), 프로필렌 글리콜 노멀프로필에테르(PnP), 테트라하이드로퓨란, 톨루엔, 자일렌, 부틸아세테이트, 에틸아세테이트, 아세톤, 메틸에틸케톤, 메틸이소부틸케톤, 메탄올, 에탄올, n-프로판올, 이소프로판올, 부탄올, 부톡시에탄올, 펜탄올, 옥탄올, 헥산, 헵탄, 에테르, 케톤 및 이들의 조합물로 구성되는 군에서 선택될 수 있고, 예를 들어, 메틸에틸케톤, 메틸아이소부틸케톤, 아세톤, 에틸아세테이트, 또는 이들의 혼합물일 수 있다.In one embodiment of the present invention, the organic solvent can be used without limitation as long as it is suitable for dissolving the solid components, and includes propylene glycol monomethyl ether acetate (PGMEA), propylene glycol monomethyl ether (PGME), and butylcell. Rosolve (BC), methylcellosolbu (MC), ethylene glycol (EG), propylene glycol (PG), N-methyl-2-pyrrolidone (NMP), dimethylacetamide (DMAc), propylene glycol diacetate (PGDA), propylene glycol normal propyl ether (PnP), tetrahydrofuran, toluene, xylene, butylacetate, ethyl acetate, acetone, methyl ethyl ketone, methyl isobutyl ketone, methanol, ethanol, n-propanol, isopropanol, butanol. , butoxyethanol, pentanol, octanol, hexane, heptane, ether, ketone, and combinations thereof, for example, methyl ethyl ketone, methyl isobutyl ketone, acetone, and ethyl acetate. , or a mixture thereof.
본 발명의 구체적인 구현예에 있어서, 상기 유기용매는 메틸에틸케톤, 메틸아이소부틸케톤, 아세톤, 에틸아세테이트를 5:3:1:1 또는 6:2:2:1 중량부를 포함하는 것일 수 있다. In a specific embodiment of the present invention, the organic solvent may include methyl ethyl ketone, methyl isobutyl ketone, acetone, and ethyl acetate in an amount of 5:3:1:1 or 6:2:2:1 by weight.
상기 퍼플루오로 다이올은 하기 화학식 1로 표시되는 화합물에서 선택되는 것일 수 있다. The perfluoro diol may be selected from compounds represented by the following formula (1).
[화학식 1] [Formula 1]
(상기 화학식 1에서 R은 -CH2(CF2)nCH2-, -CH2CF2(OCF2CF2)mOCF2CH2-, (In Formula 1, R is -CH 2 (CF 2 )nCH 2 -, -CH 2 CF 2 (OCF 2 CF 2 )mOCF 2 CH 2 -,
-CH2CF2O(CF2CF2O)nCF2CH2-, -CH2CF2O(CF2O)mCF2CH2-, 또는 -CH 2 CF 2 O(CF 2 CF 2 O)nCF 2 CH 2 -, -CH 2 CF 2 O(CF 2 O)mCF 2 CH 2 -, or
-CH2CF2O(CF2CF2O)n(CF2O)mCF2CH2-이며, 상기 n과 m은 독립적으로, 상기 n은 1 내지 8에서 선택되는 정수이고, m은 1 내지 5 에서 선택되는 정수이다).-CH 2 CF 2 O(CF 2 CF 2 O)n(CF 2 O)mCF 2 CH 2 -, where n and m are independent, n is an integer selected from 1 to 8, and m is 1 to 8. It is an integer selected from 5).
본 발명의 일 구현예에 있어서, 상기 화학식 1에서 R은 -CH2CF2O(CF2CF2O)n(CF2O)mCF2CH2-이고, 상기 n은 8이며, m은 5이다. In one embodiment of the present invention, in Formula 1, R is -CH 2 CF 2 O(CF 2 CF 2 O)n(CF 2 O)mCF 2 CH 2 -, n is 8, and m is 5. am.
본 발명의 일 구현예에 있어서, 상기 퍼플루오로 다이올은 perfluoropolyether-diol(PFPE-diol)이다.In one embodiment of the present invention, the perfluoro diol is perfluoropolyether-diol (PFPE-diol).
상기 불소계 용제는 트리플루오로노난올, 트리플루오로데칸올, 테트라플루오로노난올, 테트라플루오로데칸올, 메톡시―노나플루오로부탄 및 에톡시-노나플루오로부탄으로 이루어진 군으로부터 선택되는 하나 이상일 수 있다. The fluorine-based solvent is one selected from the group consisting of trifluorononanol, trifluorodecanol, tetrafluorononanol, tetrafluorodecanol, methoxy-nonafluorobutane, and ethoxy-nonafluorobutane. It could be more than that.
본 발명의 일 구현예에 있어서, 상기 불소계 용제는 에톡시-노나플루오로부탄이다. In one embodiment of the present invention, the fluorine-based solvent is ethoxy-nonafluorobutane.
본 발명의 일 구현예에 있어서, 상기 모노이소시아네이트 아크릴레이트 모노머는 하기 화학식 2로 표시되는 화합물인 것인, 스트레처블 디스플레이용 연신기판:In one embodiment of the present invention, the monoisocyanate acrylate monomer is a compound represented by the following formula (2): A stretched substrate for a stretchable display:
[화학식 2][Formula 2]
(상기 화학식 2에서 R1은 하기 화학식 1로 표시되는 화합물에서 선택되고, X1은 하기 화학식 3 내지 6으로 표시되는 치환기로부터 선택된다);(In Formula 2, R 1 is is selected from compounds represented by the following formula (1), and X 1 is selected from substituents represented by the following formulas (3) to (6);
[화학식 1] [Formula 1]
(상기 화학식 1에서 R은 -CH2(CF2)nCH2-, -CH2CF2(OCF2CF2)mOCF2CH2-, (In Formula 1, R is -CH 2 (CF 2 )nCH 2 -, -CH 2 CF 2 (OCF 2 CF 2 )mOCF 2 CH 2 -,
-CH2CF2O(CF2CF2O)nCF2CH2-, -CH2CF2O(CF2O)mCF2CH2-, 또는-CH 2 CF 2 O(CF 2 CF 2 O)nCF 2 CH 2 -, -CH 2 CF 2 O(CF 2 O)mCF 2 CH 2 -, or
-CH2CF2O(CF2CF2O)n(CF2O)mCF2CH2-이며, 상기 n과 m은 독립적으로, 상기 n은 1 내지 8에서 선택되는 정수이고, m은 1 내지 5 에서 선택되는 정수이다);-CH 2 CF 2 O(CF 2 CF 2 O)n(CF 2 O)mCF 2 CH 2 -, where n and m are independent, n is an integer selected from 1 to 8, and m is 1 to 8. is an integer selected from 5);
[화학식 3][Formula 3]
[화학식 4][Formula 4]
[화학식 5][Formula 5]
; 및; and
[화학식 6][Formula 6]
본 발명의 일 구현예에 있어서, 상기 모노이소시아네이트 아크릴레이트 모노머는 2-이소시아네이트에틸 메타아크릴레이트 또는 이소시아네이트에틸 아크릴레이트이다. In one embodiment of the present invention, the monoisocyanate acrylate monomer is 2-isocyanate ethyl methacrylate or isocyanate ethyl acrylate.
본 발명의 일 구현예에 있어서, 상기 다이이소시아네이트 모노머는 하기 화학식 7로 표시되는 화합물에서 선택되는 것일 수 있다:In one embodiment of the present invention, the diisocyanate monomer may be selected from compounds represented by the following formula (7):
[화학식 7][Formula 7]
(상기 화학식 7에서 R2는 하기 화학식 1로 표시되는 화합물에서 선택되고, X1은 하기 화학식 3 내지 6으로 표시되는 치환기로부터 선택되며, Y1 은 하기 화학식 8 내지 23으로 표시되는 치환기로부터 선택된다);(In Formula 7, R 2 is as follows: selected from compounds represented by Formula 1, X 1 is selected from substituents represented by Formulas 3 to 6, and Y 1 is selected from substituents represented by Formulas 8 to 23 below);
[화학식 1] [Formula 1]
(상기 화학식 1에서 R은 -CH2(CF2)nCH2-, -CH2CF2(OCF2CF2)mOCF2CH2-, (In Formula 1, R is -CH 2 (CF 2 )nCH 2 -, -CH 2 CF 2 (OCF 2 CF 2 )mOCF 2 CH 2 -,
-CH2CF2O(CF2CF2O)nCF2CH2-, -CH2CF2O(CF2O)mCF2CH2-, 또는-CH 2 CF 2 O(CF 2 CF 2 O)nCF 2 CH 2 -, -CH 2 CF 2 O(CF 2 O)mCF 2 CH 2 -, or
-CH2CF2O(CF2CF2O)n(CF2O)mCF2CH2-이며, 상기 n과 m은 독립적으로, 상기 n은 1 내지 8에서 선택되는 정수이고, m은 1 내지 5 에서 선택되는 정수이다);-CH 2 CF 2 O(CF 2 CF 2 O)n(CF 2 O)mCF 2 CH 2 -, where n and m are independent, n is an integer selected from 1 to 8, and m is 1 to 8. is an integer selected from 5);
[화학식 3][Formula 3]
; ;
[화학식 4][Formula 4]
; ;
[화학식 5][Formula 5]
; ;
[화학식 6][Formula 6]
; ;
[화학식 8] [Formula 8]
; ;
[화학식 9][Formula 9]
; ;
[화학식 10][Formula 10]
; ;
[화학식 11][Formula 11]
; ;
[화학식 12][Formula 12]
; ;
[화학식 13][Formula 13]
; ;
[화학식 14][Formula 14]
; ;
[화학식 15][Formula 15]
; ;
[화학식 16][Formula 16]
; ;
[화학식 17][Formula 17]
; ;
[화학식 18][Formula 18]
; ;
[화학식 19][Formula 19]
; ;
[화학식 20][Formula 20]
; ;
[화학식 21][Formula 21]
; ;
[화학식 22][Formula 22]
; 및 ; and
[화학식 23][Formula 23]
. .
본 발명의 일 구현예에 있어서, 상기 다이이소시아네이트 모노머는 이소포론 다이이소시아네이트(isophorone isocyanate)이다.In one embodiment of the present invention, the diisocyanate monomer is isophorone diisocyanate.
본 발명의 일 구현예에 있어서, 상기 촉매제는 당업계에서 통상적으로 사용하는 촉매제라면 특별히 제한되지 않으며, 예를 들어 아민계촉매, 유기 티탄 화합물계 및 유기 주석 화합물계 촉매에서 선택되는 어느 하나 또는 둘 이상을 사용할 수 있고, 예를 들어, 바람직하게는 유기 주석 화합물계 촉매로 디부틸 주석 디라우레이트(dibutyl tin dilaurate) 또는 디-n-부틸비스(도데실싸이오)주석(di-n-butylbis(dodecylthio)tin)을 사용할 수 있다.In one embodiment of the present invention, the catalyst is not particularly limited as long as it is a catalyst commonly used in the art, for example, one or two selected from amine-based catalysts, organotitanium compound-based and organotin compound-based catalysts. The above can be used, and for example, the organic tin compound-based catalyst is preferably dibutyl tin dilaurate or di-n-butylbis(dodecylthio)tin (di-n-butylbis). (dodecylthio)tin) can be used.
본 발명의 일 구현예에 있어서, 본 발명의 디스플레이용 연신기판의 퍼플루오로 폴리머 코팅층은 20 ㎛ 내지 1 mm의 두께를 가지고, 보다 구체적으로는 20 ㎛ 내지 800 ㎛, 20 ㎛ 내지 700 ㎛, 20 ㎛ 내지 600 ㎛, 20 ㎛ 내지 500 ㎛, 20 ㎛ 내지 350 ㎛, 20 ㎛ 내지 300 ㎛, 20 ㎛ 내지 200 ㎛, 20 ㎛ 내지 150 ㎛, 20 ㎛ 내지 100 ㎛의 두께를 가질 수 있으나, 이에 한정되는 것은 아니다.In one embodiment of the present invention, the perfluoropolymer coating layer of the stretched display substrate of the present invention has a thickness of 20 ㎛ to 1 mm, more specifically 20 ㎛ to 800 ㎛, 20 ㎛ to 700 ㎛, 20 ㎛ to 800 ㎛. It may have a thickness of ㎛ to 600 ㎛, 20 ㎛ to 500 ㎛, 20 ㎛ to 350 ㎛, 20 ㎛ to 300 ㎛, 20 ㎛ to 200 ㎛, 20 ㎛ to 150 ㎛, 20 ㎛ to 100 ㎛, but is limited thereto. becoming That is not the case.
본 발명의 일 구현예에 있어서, 본 발명의 디스플레이용 연신기판을 구성하는 상기 연신성 기판은 열경화성 폴리 우레탄, 열가소성 폴리 우레탄, 실리콘, 폴리 염화 비닐, 천연 고무, PDMS(폴리디메틸실옥산) 및 에틸렌 프로필렌 고무, 또는 이들의 조합으로 형성되는 것이나, 이에 한정되는 것은 아니다. In one embodiment of the present invention, the stretchable substrate constituting the stretched substrate for a display of the present invention is thermosetting polyurethane, thermoplastic polyurethane, silicone, polyvinyl chloride, natural rubber, PDMS (polydimethylsiloxane), and ethylene. It is formed of propylene rubber, or a combination thereof, but is not limited thereto.
본 발명의 일 구현예에 있어서, 본 발명의 스트레처블 디스플레이용 연신기판은 점착제 층을 추가로 합지(lamination)하여 제조될 수 있다. 이 경우 퍼플루오로 폴리머 코팅층, 연신성 기판, 및 점착제 층의 순서로 이루어진 3층의 스트레처블 디스플레이용 연신기판을 제작할 수 있다. In one embodiment of the present invention, the stretched substrate for a stretchable display of the present invention may be manufactured by additionally laminating an adhesive layer. In this case, a three-layer stretchable display substrate can be manufactured consisting of a perfluoropolymer coating layer, a stretchable substrate, and an adhesive layer.
본 발명의 다른 일 양태에 따르면, 본 발명은 퍼플루오로 폴리머 및 연신성 기판 제조용 폴리머를 포함하는, 스트레처블 연신기판 제조용 조성물을 제공한다.According to another aspect of the present invention, the present invention provides a composition for manufacturing a stretchable substrate, including a perfluoropolymer and a polymer for manufacturing a stretchable substrate.
본 발명의 일 구현예에 있어서, 상기 퍼플루로오 폴리머는 (a) 퍼플루오로 다이올; 불소계 용제; 유기용매; 모노이소시아네이트 아크릴레이트 모노머, 다이이소시아네이트 모노머, 또는 이들의 조합을 포함하는 반응 혼합물을 형성시키는 단계; 및 (b) 촉매제를 첨가하고 가열하는 중합반응 단계에 의해 생성된다. In one embodiment of the present invention, the perfluoro polymer is (a) perfluoro diol; fluorine-based solvent; organic solvent; forming a reaction mixture comprising monoisocyanate acrylate monomer, diisocyanate monomer, or a combination thereof; and (b) a polymerization reaction step of adding a catalyst and heating.
상기 퍼플루오로 폴리머는 상술한 본 발명의 일 양태에 따른 스트레처블 디스플레이용 연신기판을 구성하는 퍼플로오로 폴리머와 같은 구성이다. The perfluoro polymer has the same composition as the perfluoro polymer constituting the stretched substrate for a stretchable display according to an aspect of the present invention described above.
본 발명의 일 구현예에 있어서, 상기 연신성 기판 제조용 폴리머는 열경화성 폴리 우레탄, 열가소성 폴리 우레탄, 실리콘, 폴리 염화 비닐, 천연 고무, PDMS(폴리디메틸실옥산) 및 에틸렌 프로필렌 고무, 또는 이들의 조합이나, 이에 한정되는 것은 아니다. In one embodiment of the present invention, the polymer for manufacturing the stretchable substrate is thermosetting polyurethane, thermoplastic polyurethane, silicone, polyvinyl chloride, natural rubber, PDMS (polydimethylsiloxane), and ethylene propylene rubber, or a combination thereof. , but is not limited to this.
본 발명이 일 양태에 따른 조성물을 이용하면, 상기 조성물에 포함된 연신성 기판 제조용 폴리머 및 퍼플루오로 폴리머의 비중차이에 의하여 한번의 코팅으로 두 개의 층이 제조된다. When the composition according to one aspect of the present invention is used, two layers are produced with one coating due to the difference in specific gravity of the polymer for preparing a stretchable substrate and the perfluoropolymer contained in the composition.
본 발명의 상기 일 양태에 따른 스트레처블 디스플레이용 연신기판의 제조용 조성물은 상술한 본 발명의 일 양태에 따른 스트레처블 디스플레이용 연신기판을 제조하기 위하여 사용되는 것으로, 이들 발명 간에는 중복되는 구성이 존재하고 이들은 각 발명마다 동일하게 적용되며, 상기 중복되는 구성에 대해서는 명세서의 복잡성을 피하기 위하여 그 기재를 생략한다.The composition for manufacturing a stretched substrate for a stretchable display according to the above-described aspect of the present invention is used to manufacture the stretched substrate for a stretchable display according to the above-described aspect of the present invention, and the composition overlaps between these inventions. They exist and are applied equally to each invention, and description of the overlapping configurations is omitted to avoid complexity of the specification.
본 발명의 또 다른 일 양태에 따르면, 본 발명은 다음 단계를 포함하는 스트레처블 디스플레이용 연신기판의 제조방법을 제공한다:According to another aspect of the present invention, the present invention provides a method for manufacturing a stretched substrate for a stretchable display comprising the following steps:
(a) 연신성 기판 제조용 폴리머 및 퍼플루오로 폴리머를 교반하여 혼합하는 단계;(a) mixing a polymer for preparing a stretchable substrate and a perfluoropolymer by stirring;
(b) 상기 혼합물을 평면 필름 상에 코팅한 후 경화시키는 단계.(b) coating the mixture on a flat film and then curing it.
본 발명의 일 구현예에 있어서, 상기 연신성 기판 제조용 폴리머는, 모노머와 가교제, 및 경화방지제를 혼합하여 제조된다. In one embodiment of the present invention, the polymer for manufacturing the stretchable substrate is manufactured by mixing a monomer, a crosslinking agent, and a curing inhibitor.
본 발명의 일 구현예에 있어서, 상기 코팅의 두께는 20 ㎛ 내지 1 mm이다.In one embodiment of the invention, the thickness of the coating is 20 μm to 1 mm.
본 발명의 일 구현예에 있어서, 상기 경화는 100 내지 140℃에서 5 내지 30분간 가열되어 이루어진다. 보다 구체적으로, 상기 경화는 100 내지 130℃, 100 내지 120℃, 110 내지 130℃, 120 내지 130℃, 또는 115 내지 125℃에서 5 내지 30분간 가열되어 이루어질 수 있으나, 이에 한정되는 것은 아니다.In one embodiment of the present invention, the curing is performed by heating at 100 to 140°C for 5 to 30 minutes. More specifically, the curing may be accomplished by heating at 100 to 130°C, 100 to 120°C, 110 to 130°C, 120 to 130°C, or 115 to 125°C for 5 to 30 minutes, but is not limited thereto.
본 발명의 구체적인 구현예에 있어서, 상기 연신성 기판 제조용 폴리머가 PDMS인 경우, 상기 모노머는 비닐폴리실록산이다. 상기 PDMS는 비닐폴리실록산과 가교제, 경화방지제를 혼합하여 약 15분 내지 30분간 교반한 후 백금 소재의 촉매를 넣고 10분간 추가로 교반하여 제조된다.In a specific embodiment of the present invention, when the polymer for manufacturing the stretchable substrate is PDMS, the monomer is vinylpolysiloxane. The PDMS is manufactured by mixing vinyl polysiloxane, a cross-linking agent, and a curing inhibitor, stirring for about 15 to 30 minutes, then adding a catalyst made of platinum and stirring for an additional 10 minutes.
본 발명의 일 구현예에 있어서, 상기 연신성 기판 제조용 폴리머 및 퍼플루오로 폴리머는 연신성 기판 제조용 폴리머 100 중량부를 기준으로 퍼플루오로 폴리머 1 내지 20 중량부가 혼합된다. In one embodiment of the present invention, the polymer for manufacturing the stretchable substrate and the perfluoropolymer are mixed in an amount of 1 to 20 parts by weight of the perfluoropolymer based on 100 parts by weight of the polymer for manufacturing the stretchable substrate.
본 발명의 구체적인 구현예에 있어서, 상기 연신성 기판 제조용 폴리머가 PDMS인 경우, 상술한 바와 같이 비닐폴리실록산과 가교제, 경화방지제를 혼합하여 약 15분 내지 30분간 교반한 후 백금 소재의 촉매를 첨가하고, 약 5 내지 15분간 추가로 교반한 후, 퍼플루오로 폴리머를 첨가하고 약 5 내지 15분간 추가로 교반하여 연신성 기판 제조용 폴리머와 퍼플루오로 폴리머의 혼합물을 제조한다.In a specific embodiment of the present invention, when the polymer for preparing the stretchable substrate is PDMS, vinyl polysiloxane, a crosslinker, and an anti-curing agent are mixed as described above, stirred for about 15 to 30 minutes, and then a catalyst made of platinum is added. After further stirring for about 5 to 15 minutes, perfluoropolymer is added and stirred for additional about 5 to 15 minutes to prepare a mixture of the polymer for preparing a stretchable substrate and the perfluoropolymer.
본 발명의 일 구현예에 있어서, 상기 연신성 기판 제조용 폴리머와 퍼플루오로 폴리머의 혼합물은 평면 상에 소정의 두께로 코팅된 후 100 내지 140℃에서 5 내지 30분간 가열 및 건조하여 경화된다. 상기 가열 및 건조는 오븐에서 이루어질 수 있으나, 이에 한정되는 것은 아니다.In one embodiment of the present invention, the mixture of the polymer for preparing the stretchable substrate and the perfluoropolymer is coated on a flat surface to a predetermined thickness and then cured by heating and drying at 100 to 140° C. for 5 to 30 minutes. The heating and drying may be performed in an oven, but is not limited thereto.
본 발명의 제조방법에 의에 제조된 스트레처블 디스플레이용 연신기판은 상기 연신성 기판 제조용 폴리머 및 퍼플루오로 폴리머의 비중차이에 의하여 한번의 코팅으로 두 개의 층이 제조된다. The stretched substrate for a stretchable display manufactured by the manufacturing method of the present invention has two layers produced with one coating due to the difference in specific gravity between the polymer for manufacturing the stretchable substrate and the perfluoro polymer.
예컨대 연신성 기판 제조용 폴리머가 PDMS인 경우 비중이 약 1.9이고, 본 발명 퍼플루오로 폴리머의 비중은 약 1.7이므로, 한 번의 코팅으로 PDMS 층 및 퍼플루오로 폴리머 층, 두 개의 층이 제조된다.For example, when the polymer for preparing the stretchable substrate is PDMS, the specific gravity is about 1.9, and the specific gravity of the perfluoropolymer of the present invention is about 1.7, so two layers, a PDMS layer and a perfluoropolymer layer, are produced with one coating.
또한, 본 발명의 일 구현예에 있어서, 본 발명의 스트레처블 디스플레이용 연신기판은 상기 제조된 두 개의 층에 있어서, 점착제 층을 추가로 합지(lamination)하여 제조될 수 있다. 이 경우 퍼플루오로 폴리머 코팅층, 연신성 기판, 및 점착제 층의 순서로 이루어진 3층의 스트레처블 디스플레이용 연신기판을 제작할 수 있다. Additionally, in one embodiment of the present invention, the stretched substrate for a stretchable display of the present invention may be manufactured by additionally laminating an adhesive layer to the two layers manufactured above. In this case, a three-layer stretchable display substrate can be manufactured consisting of a perfluoropolymer coating layer, a stretchable substrate, and an adhesive layer.
본 발명의 상기 일 양태에 따른 스트레처블 디스플레이용 연신기판의 제조방법은 상술한 본 발명의 일 양태에 따른 스트레처블 디스플레이용 연신기판을 제조하기 위한 것으로, 상술한 본 발명의 다른 일 양태에 따른 스트레처블 디스플레이용 연신기판 제조용 조성물을 이용한 방법이므로, 이들 발명 간에는 중복되는 구성이 존재하고 이들은 각 발명마다 동일하게 적용되며, 상기 중복되는 구성에 대해서는 명세서의 복잡성을 피하기 위하여 그 기재를 생략한다.The method for manufacturing a stretched substrate for a stretchable display according to an aspect of the present invention is for manufacturing a stretched substrate for a stretchable display according to an aspect of the present invention described above, and is used in another aspect of the present invention described above. Since this is a method using a composition for manufacturing a stretched substrate for a stretchable display, there are overlapping configurations between these inventions and they are applied equally to each invention, and description of the overlapping configurations is omitted to avoid complexity of the specification. .
본 발명은 스트레처블 디스플레이 장치에 사용되는 내오염, 내스크래치성을 가지는 스트레처블 디스플레이용 연신기판에 관한 것이다. 본 발명의 조성물 및 제조방법을 이용하면, 한 번의 코팅으로 2개의 층을 가진 스트레처블 디스플레이용 연신기판을 쉽게 제조할 수 있고, 연신 기판의 최외곽 표면에 코팅된 퍼플루오로 폴리머 코팅층에 의해 내오염성 및 내스크래치성이 도입되어 스트레처블 디스플레이 터치에 의한 표면의 손상을 막을 수 있다.The present invention relates to a stretched substrate for a stretchable display having anti-fouling and scratch resistance properties used in a stretchable display device. Using the composition and manufacturing method of the present invention, a stretched substrate for a stretchable display with two layers can be easily manufactured with a single coating, and the perfluoropolymer coating layer coated on the outermost surface of the stretched substrate can be easily manufactured. Contamination resistance and scratch resistance are introduced to prevent damage to the surface caused by touching the stretchable display.
도 1은 본 발명의 3층구조의 스트레처블 디스플레이용 연신기판의 단면도이다. 상기 도 1에 나타낸 바와 같이, 디스플레이의 최외곽면에 퍼플루오로 폴리머층을 위치시켜 내오염 및 내스크래치성을 증가시키고; 연신특성을 가지는 PDMS, PU, 또는 Acryl 소재의 연신성 기판을 중간층에 배치하고; LED 및 배선 등을 고정시킬 수 있는 점착층을 합지하여 디스플레이 내부면에 위치시킨다.Figure 1 is a cross-sectional view of a stretched substrate for a three-layer stretchable display according to the present invention. As shown in FIG. 1, a perfluoropolymer layer is placed on the outermost surface of the display to increase stain resistance and scratch resistance; A stretchable substrate made of PDMS, PU, or Acryl with stretchability is placed in the middle layer; An adhesive layer capable of fixing LEDs and wiring is laminated and placed on the inner surface of the display.
이하, 실시예를 통하여 본 발명을 더욱 상세히 설명하고자 한다. 이들 실시예는 오로지 본 발명을 보다 구체적으로 설명하기 위한 것으로, 본 발명의 요지에 따라 본 발명의 범위가 이들 실시예에 의해 제한되지 않는다는 것은 당업계에서 통상의 지식을 가진 자에 있어서 자명할 것이다.Hereinafter, the present invention will be described in more detail through examples. These examples are only for illustrating the present invention in more detail, and it will be apparent to those skilled in the art that the scope of the present invention is not limited by these examples according to the gist of the present invention. .
실시예Example
본 명세서 전체에 걸쳐, 특정 물질의 농도를 나타내기 위하여 사용되는 "%"는 별도의 언급이 없는 경우, 고체/고체는 (중량/중량) %, 고체/액체는 (중량/부피) %, 그리고 액체/액체는 (부피/부피) %이다.Throughout this specification, “%” used to indicate the concentration of a specific substance means (weight/weight) % for solid/solid, (weight/volume) % for solid/liquid, and Liquid/liquid is (volume/volume) %.
제조예: 퍼플루오로 폴리머의 합성Preparation example: Synthesis of perfluoropolymer
제조예 1 Manufacturing Example 1
퍼플루오로 다이올 10 중량부에 불소계 용제(ethoxynonafluorobutane (C4F9OC2H5)) 45 중량부와 메틸에틸케톤, 메틸아이소부틸케톤, 아세톤, 에틸아세테이트를 5:3:1:1 또는 6:2:2:1 중량부를 첨가하고, 2-이소시아네이트에틸 메타아크릴레이트를 25 중량부 첨가하고 질소 가스 분위기에서 촉매제로서 디부틸 주석 디라우레이트 0.01 중량부를 첨가하고 20-50분 동안 상온 교반하였다. 이어서 온도를 최고 100℃까지 천천히 올려 촉매제 0.01 중량부를 첨가하고 반응 시간을 확인하여 우레아 반응이 끝날 때까지 중합을 실시하였다. 상기 중합은 유리반응기에서 200-300 rpm으로 교반시키며 실시하였다.To 10 parts by weight of perfluoro diol, 45 parts by weight of a fluorine-based solvent (ethoxynonafluorobutane (C 4 F 9 OC 2 H 5 )) and methyl ethyl ketone, methyl isobutyl ketone, acetone, and ethyl acetate are mixed in a ratio of 5:3:1:1 or 6:2:2:1 parts by weight were added, 25 parts by weight of 2-isocyanate ethyl methacrylate was added, and 0.01 parts by weight of dibutyl tin dilaurate was added as a catalyst in a nitrogen gas atmosphere and stirred at room temperature for 20-50 minutes. . Then, the temperature was slowly raised to a maximum of 100°C, 0.01 parts by weight of catalyst was added, the reaction time was checked, and polymerization was performed until the urea reaction was completed. The polymerization was carried out in a glass reactor with stirring at 200-300 rpm.
제조예 2Production example 2
퍼플루오로 다이올(Fomblin D2, Solvay) 10 중량부에 불소계 용제(ethoxynonafluorobutane (C4F9OC2H5)) 45 중량부와 메틸에틸케톤, 메틸아이소부틸케톤, 아세톤, 에틸아세테이트를 5:3:1:1 또는 6:2:2:1 중량부를 첨가하고, 다이이소시아네이트 모노머(TCI) 6 중량부 첨가하고 질소 가스 분위기에서 촉매제로서 디부틸 주석디라우레이트 0.01 중량부를 첨가하고 20-50분 동안 상온 교반하였다. 이어서 온도를 최고 100℃까지 천천히 올려 반응 시간을 확인하여 우레아 반응이 끝날 때 까지중합을 실시하였다. 1차 중합 실시 후 2-이소시아네이트에틸 메타아크릴레이트(TCI)를 25 중량부 첨가하고 질소 가스 분위기에서 촉매제 0.01 중량부를 첨가한 다음, 20-50분 동안 상온 교반하였다. 이어서 온도를 최고 100℃까지 천천히 올려 반응 시간을 확인하여 우레아 반응이 끝날 때까지 중합을 실시하였다. 상기 중합은 유리반응기에서 200-300 rpm으로 교반시키며 실시하였다.10 parts by weight of perfluoro diol (Fomblin D2, Solvay) is mixed with 45 parts by weight of a fluorine-based solvent (ethoxynonafluorobutane (C 4 F 9 OC 2 H 5 )) and 5 parts by weight of methyl ethyl ketone, methyl isobutyl ketone, acetone, and ethyl acetate. Add 3:1:1 or 6:2:2:1 parts by weight, add 6 parts by weight of diisocyanate monomer (TCI), add 0.01 parts by weight of dibutyl tindilaurate as a catalyst in a nitrogen gas atmosphere, and stir for 20-50 minutes. The mixture was stirred at room temperature. Then, the temperature was slowly raised to a maximum of 100°C, the reaction time was checked, and polymerization was performed until the urea reaction was completed. After the first polymerization, 25 parts by weight of 2-isocyanate ethyl methacrylate (TCI) was added, 0.01 parts by weight of a catalyst was added in a nitrogen gas atmosphere, and the mixture was stirred at room temperature for 20-50 minutes. Then, the temperature was slowly raised to a maximum of 100°C, the reaction time was checked, and polymerization was performed until the urea reaction was completed. The polymerization was carried out in a glass reactor with stirring at 200-300 rpm.
제조예 3Production example 3
퍼플루오로 다이올(Fomblin D2, Solvay) 20 중량부에 불소계 용제(ethoxynonafluorobutane (C4F9OC2H5)) 45 중량부와 메틸에틸케톤, 메틸아이소부틸케톤, 아세톤, 에틸아세테이트를 5:3:1:1 또는 6:2:2:1 중량부를 첨가하고, 다이이소시아네이트 모노머 12 중량부 첨가하고 질소 가스 분위기에서 촉매제로서 디부틸 주석디라우레이트 0.02 중량부를 첨가하고 20-50분 동안 상온 교반하였다. 이어서 온도를 최고 100℃까지 천천히 올려 반응 시간을 확인하여 우레아 반응이 끝날 때 까지중합을 실시하였다. 1차 중합 실시 후 2-이소시아네이트에틸 메타아크릴레이트를 25 중량부 첨가하고 질소 가스 분위기에서 촉매제 0.02 중량부를 첨가한 다음, 20-50분 동안 상온 교반하였다. 이어서 온도를 천천히 최고 100℃까지 올려 반응 시간을 확인하여 우레아 반응이 끝날 때까지 중합을 실시하였다. 상기 중합은 유리반응기에서 200-300 rpm으로 교반시키며 실시하였다.20 parts by weight of perfluoro diol (Fomblin D2, Solvay) is mixed with 45 parts by weight of a fluorine-based solvent (ethoxynonafluorobutane (C 4 F 9 OC 2 H 5 )) and 5 parts by weight of methyl ethyl ketone, methyl isobutyl ketone, acetone, and ethyl acetate. Add 3:1:1 or 6:2:2:1 parts by weight, add 12 parts by weight of diisocyanate monomer, add 0.02 parts by weight of dibutyl tin dilaurate as a catalyst in a nitrogen gas atmosphere, and stir at room temperature for 20-50 minutes. did. Then, the temperature was slowly raised to a maximum of 100°C, the reaction time was checked, and polymerization was performed until the urea reaction was completed. After the first polymerization, 25 parts by weight of 2-isocyanate ethyl methacrylate was added, 0.02 parts by weight of a catalyst was added in a nitrogen gas atmosphere, and the mixture was stirred at room temperature for 20-50 minutes. Then, the temperature was slowly raised to a maximum of 100°C, the reaction time was checked, and polymerization was performed until the urea reaction was completed. The polymerization was carried out in a glass reactor with stirring at 200-300 rpm.
제조예 4Production example 4
퍼플루오로 다이올(Fomblin D2, Solvay) 30 중량부에 불소계 용제(ethoxynonafluorobutane (C4F9OC2H5)) 45 중량부와 메틸에틸케톤, 메틸아이소부틸케톤, 아세톤, 에틸아세테이트를 5:3:1:1 또는 6:2:2:1 중량부를 첨가하고, 다이이소시아네이트 모노머 18 중량부 첨가하고 질소 가스 분위기에서 촉매제로서 디부틸 주석디라우레이트 0.03 중량부를 첨가하고 20-50분 동안 상온 교반하였다. 이어서 온도를 천천히 최고 100℃까지 올려 반응 시간을 확인하여 우레아 반응이 끝날 때까지 중합을 실시하였다. 1차 중합 실시 후 2-이소시아네이트에틸 메타아크릴레이트를 25 중량부 첨가하고 질소 가스 분위기에서 촉매제 0.03 중량부를 첨가한 다음, 20-50분 동안 상온 교반하였다. 이어서 온도를 천천히 최고 100℃까지 올려 반응 시간을 확인하여 우레아 반응이 끝날 때까지 중합을 실시하였다. 상기 중합은 유리반응기에서 200-300 rpm으로 교반시키며 실시하였다.30 parts by weight of perfluoro diol (Fomblin D2, Solvay) is mixed with 45 parts by weight of a fluorine-based solvent (ethoxynonafluorobutane (C 4 F 9 OC 2 H 5 )) and 5 parts by weight of methyl ethyl ketone, methyl isobutyl ketone, acetone, and ethyl acetate. Add 3:1:1 or 6:2:2:1 parts by weight, add 18 parts by weight of diisocyanate monomer, add 0.03 parts by weight of dibutyl tin dilaurate as a catalyst in a nitrogen gas atmosphere, and stir at room temperature for 20-50 minutes. did. Then, the temperature was slowly raised to a maximum of 100°C, the reaction time was checked, and polymerization was performed until the urea reaction was completed. After the first polymerization, 25 parts by weight of 2-isocyanate ethyl methacrylate was added, 0.03 parts by weight of a catalyst was added in a nitrogen gas atmosphere, and the mixture was stirred at room temperature for 20-50 minutes. Then, the temperature was slowly raised to a maximum of 100°C, the reaction time was checked, and polymerization was performed until the urea reaction was completed. The polymerization was carried out in a glass reactor with stirring at 200-300 rpm.
상기 중합비(중량비)는 표 1과 같았다.The polymerization ratio (weight ratio) was as shown in Table 1.
(Fomblin D2, Solvay)Perfluorodiol
(Fomblin D2, Solvay)
(디부틸 주석디라우레이트)catalyst
(Dibutyl tindilaurate)
(TCI)Monoisocyanate Acrylate Monomer
(TCI)
비교예 1: 일반 실리콘 연신기판의 제조(종래 기술)Comparative Example 1: Manufacturing of a general silicone stretched substrate (prior art)
500 ml 용기에 비닐폴리실록산과 가교제, 경화방지제(1-Ethynyl-1-cyclohexanol)를 투입한 뒤 교반기를 사용하여 500 rpm으로 20 분간 교반하였다. 여기에 백금 촉매를 투입하고 교반기를 사용하여 10분간 교반한 뒤 진공에서 10분간 탈포하여 기판 제조를 위한 실리콘 조성물을 제조한 뒤 폴리에틸렌 필름 위에 코팅바를 사용하여 500 μm 두께로 코팅한 후 120℃ 오븐에서 10분간 경화시켜 스트레처블 연신기판을 제조하였다. Vinyl polysiloxane, cross-linking agent, and anti-hardening agent (1-Ethynyl-1-cyclohexanol) were added to a 500 ml container and stirred at 500 rpm for 20 minutes using a stirrer. A platinum catalyst was added here, stirred for 10 minutes using a stirrer, and degassed in a vacuum for 10 minutes to prepare a silicone composition for manufacturing a substrate. Then, it was coated on a polyethylene film to a thickness of 500 μm using a coating bar and placed in an oven at 120°C. A stretchable stretched substrate was manufactured by curing for 10 minutes.
상기에서 사용된 원료의 조성은 하기 표 2과 같았다. The composition of the raw materials used above was as shown in Table 2 below.
실시예 1 내지 실시예 4: 다층구조의 스트레처블 디스플레이용 연신기판의 제조Examples 1 to 4: Manufacturing of stretched substrate for multi-layered stretchable display
상기 비교예 1과 같이 500 ml 용기에 비닐폴리실록산과 가교제, 경화방지제(1-Ethynyl-1-cyclohexanol)를 투입한 뒤 교반기를 사용하여 500 rpm으로 20 분간 교반하였다. 여기에 백금 촉매를 투입하고 교반기를 사용하여 10분간 교반하여 제조한 실리콘 코팅액에 제조예 1 내지 4에서 제조된 퍼플루오로 폴리머 10 중량부를 혼합하여 10분간 교반하여, 본 발명의 스트레처블 디스플레이용 연신기판 제조용 조성물을 제조하였다. 제조된 상기 조성물을 폴리에틸렌 필름 위에 코팅바를 사용하여 500 μm 두께로 코팅하였다. 상기 코팅 층은 본 발명의 스트레처블 디스플레이용 연신기판 제조용 조성물에 포함된 연신기판 제조용 폴리머(PDMS) 및 퍼플루오로 폴리머의 비중차이에 의해 2 층으로 나뉘고, 이를 120℃ 오븐에서 10간 경화시켜 본 발명의 스트레처블 디스플레이용 연신기판을 제조하였다. 상기에서 사용된 원료의 조성은 하기 표 3 같았다.As in Comparative Example 1, vinyl polysiloxane, a cross-linking agent, and an anti-hardening agent (1-Ethynyl-1-cyclohexanol) were added to a 500 ml container and stirred at 500 rpm for 20 minutes using a stirrer. A platinum catalyst was added here and stirred for 10 minutes using a stirrer, and 10 parts by weight of the perfluoropolymer prepared in Preparation Examples 1 to 4 was mixed with the prepared silicone coating solution and stirred for 10 minutes to obtain a silicone coating solution for the stretchable display of the present invention. A composition for manufacturing a stretched substrate was prepared. The prepared composition was coated on a polyethylene film to a thickness of 500 μm using a coating bar. The coating layer is divided into two layers due to the difference in specific gravity between the polymer for manufacturing stretched substrates (PDMS) and the perfluoropolymer included in the composition for manufacturing stretched substrates for stretchable displays of the present invention, and cured in an oven at 120°C for 10 minutes. A stretched substrate for a stretchable display of the present invention was manufactured. The composition of the raw materials used above was as shown in Table 3 below.
(Toluene)menstruum
(Toluene)
실험예 1: 투과율(%) 및 헤이즈(%)의 측정Experimental Example 1: Measurement of transmittance (%) and haze (%)
비교예 및 각 실시예에서 제조한 연신기판 필름의 시편을 채취하여 Nippon Denshoku사의 COH-400을 사용하여 투과율과 Haze를 측정하였다. 비교예와 실시예를 통하여 제조한 500 ㎛의 연신기판 필름을 시편의 제조방향 처음으로 300 mm 부분을 잘라내고 다시 그 끝 부분에서 20 mm 안쪽의 부위에서 100 mm X 100 mm 의 사각으로 잘라내었다. 광원이 할로겐 램프인 Nippon Denshoku사의 COH-400을 사용하여 Single 빔 가시광선 전파장의 투과율과 Haze를 측정하였다.Samples of the stretched substrate films manufactured in Comparative Examples and each Example were collected, and transmittance and Haze were measured using Nippon Denshoku's COH-400. The 500 ㎛ stretched substrate film manufactured through Comparative Examples and Examples was cut at the beginning of a 300 mm portion in the manufacturing direction of the specimen, and then cut into a square of 100 mm The transmittance and haze of the single beam visible light wave field were measured using Nippon Denshoku's COH-400, a halogen lamp light source.
실험예 2: 접촉각Experimental Example 2: Contact angle
물의 부피를 3 ㎕ 크기로 600 ㎕/min 시료 중간에 떨어뜨리고 3초후 접촉각을 측정하였다. 50 mm X 50 mm 크기로 잘라낸 연신기판 위에 물의 부피를 3 ㎕ 크기로 600 ㎕/min 시료 중간에 떨어뜨리고 3초 후 정지된 물방울과 연신기판 필름사이의 접촉각을 Surfacetech사의 GS-Mini 모델을 사용하여 측정하였다.A volume of 3 ㎕ water was dropped into the middle of the sample at 600 ㎕/min, and the contact angle was measured 3 seconds later. On a stretched substrate cut to the size of 50 mm Measured.
실험예 3: 코팅 두께의 측정Experimental Example 3: Measurement of coating thickness
두께측정기(Mitutoyo, 547 thickness gauge)로 압력 20±0.2 kPa로 5초 동안 가압한 후 제품의 제조방향으로 처음 300 mm 부분은 잘라내고, 다시 그 끝 부분에서 20 mm 안쪽인 부위에서 양끝으로 각각 나비(폭)의 10% 안쪽으로 들어간 지점 2곳과 그 사이를 9등한 지점 8곳을 합한 10곳을 0.01 mm 까지 두께를 측정하여 그 측정치의 평균치를 구하였다. After pressurizing with a thickness gauge (Mitutoyo, 547 thickness gauge) for 5 seconds at a pressure of 20 ± 0.2 kPa, the first 300 mm part is cut in the manufacturing direction of the product, and then again from the area 20 mm in from the end to both ends. The thickness was measured to 0.01 mm at 10 points, including 2 points within 10% of the width and 8 points between them, and the average of the measurements was obtained.
상기 실험예 1 내지 3의 결과는 표 4에 나타내었다.The results of Experimental Examples 1 to 3 are shown in Table 4.
상기 표 4에 나타낸 바와 같이, 본 발명의 퍼플루오로 폴리머를 포함하는 스트레처블 디스플레이용 연신기판은 물접촉각이 높아져 내오염성 및 내스크래치성이 우수하고, 투과율이 증가하고 헤이즈가 감소하므로 디스플레이로서의 광학적 성능이 우수해짐을 알 수 있다. As shown in Table 4, the stretched substrate for a stretchable display containing the perfluoropolymer of the present invention has an increased water contact angle, has excellent stain resistance and scratch resistance, and has increased transmittance and reduced haze, so it can be used as a display. It can be seen that optical performance is improved.
100: 퍼플루오로 폴리머를 포함하는 코팅층
200: 연신성을 갖는 연신성 기판
300: 점착제 층100: Coating layer containing perfluoropolymer
200: Stretchable substrate with stretchability
300: Adhesive layer
Claims (17)
(a) 연신성 기판 제조용 폴리머 및 퍼플루오로 폴리머를 교반하여 혼합하는 단계; 및
(b) 상기 혼합물을 평면 필름 상에 코팅한 후 2층으로 분리된 코팅층을 경화시키는 단계.
여기에서 상기 연신성 기판 제조용 폴리머 및 퍼플루오로 폴리머는 비중이 서로 상이함.
Method for manufacturing a stretched substrate for a stretchable display comprising the following steps:
(a) mixing a polymer for preparing a stretchable substrate and a perfluoropolymer by stirring; and
(b) coating the mixture on a flat film and then curing the coating layer separated into two layers.
Here, the polymer for manufacturing the stretchable substrate and the perfluoro polymer have different specific gravity.
The method of claim 1, wherein the polymer for producing the stretchable substrate is thermosetting polyurethane, thermoplastic polyurethane, silicone, polyvinyl chloride, natural rubber, PDMS (polydimethylsiloxane), and ethylene propylene rubber, or a combination thereof. .
(b) 촉매제를 첨가하고 가열하는 중합반응 단계에 의해 생성된 것인, 제조방법.
The method of claim 1, wherein the perfluoro polymer is (a) perfluoro diol; fluorine-based solvent; organic solvent; forming a reaction mixture comprising monoisocyanate acrylate monomer, diisocyanate monomer, or a combination thereof; and
(b) A production method produced by a polymerization reaction step of adding a catalyst and heating.
[화학식 1]
(상기 화학식 1에서 R은 -CH2(CF2)nCH2-, -CH2CF2(OCF2CF2)mOCF2CH2-,
-CH2CF2O(CF2CF2O)nCF2CH2-, -CH2CF2O(CF2O)mCF2CH2-, 또는
-CH2CF2O(CF2CF2O)n(CF2O)mCF2CH2-이며, 상기 n과 m은 독립적으로, 상기 n은 1 내지 8에서 선택되는 정수이고, m은 1 내지 5 에서 선택되는 정수이다).
The preparation method according to claim 3, wherein the perfluoro diol is selected from compounds represented by the following formula (1):
[Formula 1]
(In Formula 1, R is -CH2(CF2)nCH2-, -CH2CF2(OCF2CF2)mOCF2CH2-,
-CH2CF2O(CF2CF2O)nCF2CH2-, -CH2CF2O(CF2O)mCF2CH2-, or
-CH2CF2O(CF2CF2O)n(CF2O)mCF2CH2-, where n and m are independent, n is an integer selected from 1 to 8, and m is an integer selected from 1 to 5.
The method of claim 3, wherein the fluorine-based solvent is trifluorononanol, trifluorodecanol, tetrafluorononanol, tetrafluorodecanol, methoxy-nonafluorobutane, and ethoxy-nonafluorobutane. A manufacturing method, which is at least one selected from the group consisting of.
The method of claim 3, wherein the organic solvent is methyl ethyl ketone, methyl isobutyl ketone, acetone, ethyl acetate, or a mixture thereof.
[화학식 2]
(상기 화학식 2에서 R1은 하기 화학식 1로 표시되는 화합물에서 선택되고, X1은 하기 화학식 3 내지 6으로 표시되는 치환기로부터 선택된다);
[화학식 1]
(상기 화학식 1에서 R은 -CH2(CF2)nCH2-, -CH2CF2(OCF2CF2)mOCF2CH2-,
-CH2CF2O(CF2CF2O)nCF2CH2-, -CH2CF2O(CF2O)mCF2CH2-, 또는
-CH2CF2O(CF2CF2O)n(CF2O)mCF2CH2-이며, 상기 n과 m은 독립적으로, 상기 n은 1 내지 8에서 선택되는 정수이고, m은 1 내지 5 에서 선택되는 정수이다);
[화학식 3]
;
[화학식 4]
;
[화학식 5]
; 및
[화학식 6]
.
The method of claim 3, wherein the monoisocyanate acrylate monomer is a compound represented by the following formula (2):
[Formula 2]
(In Formula 2, R1 is selected from compounds represented by Formula 1 below, and X1 is selected from substituents represented by Formulas 3 to 6 below);
[Formula 1]
(In Formula 1, R is -CH2(CF2)nCH2-, -CH2CF2(OCF2CF2)mOCF2CH2-,
-CH2CF2O(CF2CF2O)nCF2CH2-, -CH2CF2O(CF2O)mCF2CH2-, or
-CH2CF2O(CF2CF2O)n(CF2O)mCF2CH2-, where n and m are independently an integer selected from 1 to 8, and m is an integer selected from 1 to 5);
[Formula 3]
;
[Formula 4]
;
[Formula 5]
; and
[Formula 6]
.
[화학식 7]
(상기 화학식 7에서 R2는 하기 화학식 1로 표시되는 화합물에서 선택되고, X1은 하기 화학식 3 내지 6으로 표시되는 치환기로부터 선택되며, Y1 은 하기 화학식 8 내지 23으로 표시되는 치환기로부터 선택된다);
[화학식 1]
(상기 화학식 1에서 R은 -CH2(CF2)nCH2-, -CH2CF2(OCF2CF2)mOCF2CH2-,
-CH2CF2O(CF2CF2O)nCF2CH2-, -CH2CF2O(CF2O)mCF2CH2-, 또는
-CH2CF2O(CF2CF2O)n(CF2O)mCF2CH2-이며, 상기 n과 m은 독립적으로, 상기 n은 1 내지 8에서 선택되는 정수이고, m은 1 내지 5 에서 선택되는 정수이다);
[화학식 3]
;
[화학식 4]
;
[화학식 5]
;
[화학식 6]
;
[화학식 8]
;
[화학식 9]
;
[화학식 10]
;
[화학식 11]
;
[화학식 12]
;
[화학식 13]
;
[화학식 14]
;
[화학식 15]
;
[화학식 16]
;
[화학식 17]
;
[화학식 18]
;
[화학식 19]
;
[화학식 20]
;
[화학식 21]
;
[화학식 22]
; 및
[화학식 23]
.
The production method according to claim 3, wherein the diisocyanate monomer is selected from compounds represented by the following formula (7):
[Formula 7]
(In Formula 7, R2 is selected from compounds represented by Formula 1 below, X1 is selected from substituents represented by Formulas 3 to 6 below, and Y1 is selected from substituents represented by Formulas 8 to 23 below);
[Formula 1]
(In Formula 1, R is -CH2(CF2)nCH2-, -CH2CF2(OCF2CF2)mOCF2CH2-,
-CH2CF2O(CF2CF2O)nCF2CH2-, -CH2CF2O(CF2O)mCF2CH2-, or
-CH2CF2O(CF2CF2O)n(CF2O)mCF2CH2-, where n and m are independently an integer selected from 1 to 8, and m is an integer selected from 1 to 5);
[Formula 3]
;
[Formula 4]
;
[Formula 5]
;
[Formula 6]
;
[Formula 8]
;
[Formula 9]
;
[Formula 10]
;
[Formula 11]
;
[Formula 12]
;
[Formula 13]
;
[Formula 14]
;
[Formula 15]
;
[Formula 16]
;
[Formula 17]
;
[Formula 18]
;
[Formula 19]
;
[Formula 20]
;
[Formula 21]
;
[Formula 22]
; and
[Formula 23]
.
The manufacturing method according to claim 1, wherein the coating has a thickness of 20 μm to 1 mm.
The manufacturing method according to claim 1, wherein the curing is performed by heating at 100 to 140° C. for 5 to 30 minutes.
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